JP2665892B2 - Concentrates of additives for lubricating and fuel oils - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] FIELD OF THE INVENTION This invention relates to fuel and lubricating oil compositions.
Additive containing an oil-soluble dispersant useful as an additive
It relates to thick articles, their production and use. This variance
The agent is a dicarboxylic acid substituted with a high molecular weight hydrocarbon group,
Anhydride or esterWhen,AMin, alcohol, amino
RucolOr mixtures thereofWhenofreactionProductThis
It can be further processed, e.g.
Can be. High molecular weight hydrocarbon groups are from about 1,500 to
It has a number average molecular weight (Mn) of 5,000. This addition
The agent is dical per high molecular weight hydrocarbon used in the reaction.
About 1.05 to 1.25 of a boric acid, anhydride or ester moiety
Number (functional number). Thus, the additive
Minimizes viscosity-improving action while having improved dispersibility
Oil additive. [0002] BACKGROUND OF THE INVENTION U.S. Pat. No. 4,234,435
Has Mn of 1,300 to 5,000 as an oil additive.
Derived from polyalkenes having
Poly-containing at least 1.3 dicarboxylic acid groups
Alkene-substituted dicarboxylic acids are disclosed. Canada Special
No. 895,398, 700 to 10,000
1 to 1.5 moles of 1 mole of unsaturated hydrocarbon having
With chloro-substituted maleic or fumaric acid of
This material can then be further reacted with alcohol.
Is disclosed. [0003] US Pat. No. 3,927,041 discloses a touch panel.
5-200 ppm of 1,3-dibromo-5,5 as a medium
-A molecular weight of 300 to containing dialkylhydantoin
3,000 1 mole of polybutene is from 0.8 to 5 in general
1.05 to 1.15 mol of dicarboxylic acid or anhydride
In the petroleum product itself or in the form of esters,
Substances that can be used as imides, imides and amidines
Is disclosed. US Patent No. 3,21
No. 7,707, especially the molecular weight up to 50,000
250-3,000 polyolefins and each polymer molecule
Depending on whether there is more than one succinic anhydride group in it
Chlorine in one or more moles of a mixture with maleic anhydride
Is disclosed. [0004] US Patent Nos. 4,113,639 and
No. 4,116,876 has 1,300 alkenyl groups
Molecular weight and a saponification value of 103 (about 1.
Alkenyl anhydride having 3 succinic anhydride units)
Examples of citric acid are disclosed. This alkenyl anhydrous amber
The acid can be reacted with polyamine and then with boric acid
(U.S. Pat. No. 4,113,639) or aminoal
To form oxazolines (US Patent No.
No. 4,116,876) and then by reaction with boric acid
It can also be boronized. U.S. Pat. No. 4,062,
No. 186 shows that in Example 13, about 1,300 molecules
Amount and a saponification value of about 100 (about 1.2 per alkenyl group).
Polyisobutenyl having 5 succinic anhydride units)
Indicating succinic anhydride. US Patent No. 4,123,3
No. 73 has a molecular weight of about 1,400 in Example 3.
And a saponification value of about 80 (approximately 1.0
Polyisobutenyl compound having 7 succinic anhydride units)
Shows succinic anhydride. [0005] Further related prior art is the following US patents:
3,087,936; 3,131,150; 3,15
4,560; 3,172,892; 3,198,73
6; 3,219,666; 3,231,587; 3,2
35,484; 3,269,946; 3,272,74
3, 3,272,746; 3,278,550; 3,2
84,409; 3,284,410; 3,288,71
4: 3,403, 102; 3,562,159; 3,5
76,743; 3,632,510; 3,836,47
0; 3,836,471; 3,383,050; 3,8
38,052; 3,879,308; 3,912,76
4, 3,927,041; Re. 26,330; 4,1
10,349; 4,113,639; 4,151,17
3, 4,195,976; and British Patent 1,368,
277 and 1,398,008. [0006]Summary of the Invention The present invention relates to a method wherein
Preferably 1.06 to 1.20, for example 1.10 to 1.2
0 dicarboxylic acids, anhydrides or ester moieties preferred
Is a number average molecular weight 1,50 substituted with an acid or anhydride moiety.
Hydrocarby comprising 0 to 5,000 polyolefin
Substitution C₄~ C₁₀Dicarboxylic acid, anhydride or ester
materialAnd amine, alcohol, amino alcohol or this
Consisting of the reaction products of these mixturesContains oil-soluble dispersant
Additive concentrates. This acid, anhydride
Alternatively, the ester material may itself be, for example, U.S. Pat.
No. 288,714 (where the conventional acylating agent is dispersed
US Pat.
No. 714,042 (where the overbased metal complex is treated
Conventional acylating agents have been used to
Known polyolefin-substituted dicarboxylic acids
As an additive in the same manner as an acid or anhydride acylating agent
It is useful as a dispersant. Also,ThisThe substance is overbased
US specialty where a water-soluble detergent is being treated with an acylating agent.
Used in the mode described in JP 3,965,017
Can alsoTo.OrComb, if acid, anhydride or ester
If one wants to further react the substance, for example neutralize it,
Is from at least 50% of the acid units to all of the acid units.
The proportion is reacted. [0007]Detailed description of the invention The substance of the present invention has a di / hydrocarbon moiety used in the reaction.
Functionality of 1.3 or more carboxylic acid, anhydride or ester group
Compared to the above prior art disclosure having other
Their effectiveness in combination with a low degree of interaction with the drug
Therefore, it differs from the prior art. Using the additive of the present invention
Suitable for gasoline and diesel engines, etc.
Lubricating oil compositions such as automatic transmission fluids, heavy duty oils
Can be prepared. Gasoline and diesel
Using the same lubricating oil composition for both engines
Can be used to prepare all-purpose crankcase oil
You. These lubricating oil compositions are conventionally used in the compositions.
Several different types of additives to provide the properties required for
Contains additives. These types of additives include viscosity
Index improver, antioxidant, corrosion inhibitor, detergent, dispersion
Agents, pour point depressants, antiwear additives and the like. In preparing a lubricating oil composition, additives are used.
In hydrocarbon oils such as mineral lubricating oils or other suitable solvents
10 to 80% by weight, for example, 20 to 80% by weight
It is common practice to introduce it in the form of a concentrate. Through
Usually, these concentrates are used in final lubricants such as crankcases.
Additive package 1 for preparing sumota oil
3 to 40 parts by weight, for example, 5 to 20 parts by weight of lubricating oil
Can be Of course, the purpose of the concentrate is final
Facilitates dissolution or dispersion in the mixture and
It is to reduce the difficulty and inconvenience of handling quality. Or
A metal hydrocarbyl sulfonate or a metal alcohol
Kilfenate is usually used, for example, in lubricating oil fractions.
It is used in the form of a 40-50% by weight concentrate. Usually
Suitable for the preparation of lubricating oil mixtures containing several types of additives.
Therefore, each additive is distributed separately in the form of a concentrate in oil.
If they do, no problem arises. However, many
In some cases, the supplier of the additive may be a hydrocarbon oil or other suitable
Additives containing multiple additives in a single concentrate in the appropriate solvent
Hope to make “packages” available. Some
Additives tend to react with each other in oil concentrates
is there. 1.3 or more dicarboxylic acid moieties per hydrocarbon molecule
The dispersant having a functionality (ratio) of
Interact with and mix with various other ingredients, especially overbased metal detergents.
Viscosity rise at the time (followed by a viscosity increase over time
Cause gelation of the mixture in some cases)
Found to cause. This increase in viscosity
Pumping, mixing and handling may be hindered. Pa
The package is further diluted with more diluent oil and its viscosity
Can offset the interaction effect by lowering
However, this dilution increases transport, storage and other handling costs.
Reduces the economics of using the package
Let it. The present invention having a functionality lower than 1.25: 1
Material minimizes this viscosity interaction and is effective
Form additives. The compositions described herein may be used in engines
Hydrocarbons required to maintain dispersant oil solubility during operation
Providing a low molecular weight polymer with less acylation units per polyamine
Provide additional improvements in that An example
For example, functional groups having 1.3 or more dicarboxylic acid groups per polymer
Polybutene acylating agent having 4 to 7 nitrogen atoms per molecule
Condensed with atom-containing polyethylene amines?
Typical dispersants derived from gasoline and diesel
Sufficient oil dissolution for proper dispersibility in the engine
Two or more acyls per polyamine to provide
Requires a chemical unit. Lower the functionality below 1.25
Yields a low relative stoichiometry of the acylating agent per polyamine
Required ratio of oil-soluble polymer per polyamine
I will. Thus, polybutenea having a functionality of 1.05
The silylating agent is 1.5 to 1 with 5-nitrogen polyethyleneamine.
Dispersants derived from condensing in a ratio of 1.4
Polybutene acylating agent having a functionality of
Derived from condensing with a 2: 1 ratio
It has about the same ratio of non-polar groups to polar groups as the agent. Former
The composition has a much lower viscosity and reduced compared to the latter
Shows the interaction. [0009]Hydrocarbyl dicarboxylic acid substances Long chain hydrocarbyl substituted dica used in the present invention
The rubonic acid material, i.e., acid or anhydride or ester, is
1.05 to 1.25 per mole of olefin, preferably
1.06-1.20 e.g. 1.10-1.20 moles of α
-Or β-unsaturated C_Four ~ C_TenDicarboxylic acid or anhydrous
Or its ester such as fumaric acid, itaconic acid, male
Formic acid, maleic anhydride, chlormaleic acid, fumaric acid
Long-chain carbon substituted with dimethyl, chloromaleic anhydride, etc.
Hydrogen hydrides generally include polyolefins. Unsaturated zika
Preferred olefin polymers for reaction with rubonic acid are polyolefins.
Ratio C_Two ~ C_TenFor example, C_Two ~ C_Five Monoolefin
It is a polymer containing. Such olefins include ethylene
Propylene, butylene, isobutylene, pentene,
Octene-1, styrene and the like. The polymer is
Homopolymers such as lysobutylene and ethylene / pro
Pyrene copolymer, butylene / isobutylene copolymer,
Olef such as propylene / isobutylene copolymer
It may be a copolymer of two or more kinds of quinone. Other copolymer
Is a small molar amount of the monomer of the copolymer, for example, 1 to 40
Mol% is C_Four ~ C₁₈Such as non-conjugated diolefins
For example, isobutylene / butadiene copolymer or d.
Tylene / propylene / 1,4-hexadiene copolymer, etc.
Is mentioned. In some cases, the olefin polymer is completely
Saturates, for example, as regulators for controlling molecular weight
Made by Ziegler-Natus synthesis using hydrogen
Or an ethylene / propylene copolymer. me
Fin polymers are typically from about 1,500 to about 5,000.
Preferably number average within the range of about 1,600 to about 3,000
Has a molecular weight. Particularly useful olefin polymers are about
A number average molecular weight in the range of 1,500 to about 2,500, and
It has about one terminal double bond per polymer chain. In the present invention
A particularly useful starting material for the high capacity dispersants thus made
The quality is polyisobutylene. Number average of such polymers
Quantities can be measured by several known techniques.
You. A convenient method for such measurements is to use molecular weight distribution data.
Gel permeation chromatography (G
PC). WW
C, Jay Jay Kirkland and Dee Dee
・ Bree's “Modern Size Exclusion LiquidChroma
tography "(John Wheelie and Sons, D
New York, 1979). The olefin polymer is represented by C_Four ~_TenUnsaturated dical
The method for reacting with boric acid, anhydride or ester is
Known in the art. For example, US Pat.
Nos. 61,673 and 3,401,118.
Olefin polymer and dicarboxylic acid material
Heating together can cause a thermal "ene" reaction
it can. Alternatively, the olefin polymer is first halogenated
For example, chlorine or bromine can be
At a temperature of 100-250 ° C, for example 140-225 ° C
About 0.5 to 10 hours, preferably 1 to 7 hours
About 1 to 8, preferably 3 to 7, based on the weight of the polymer.
Chlorinating or brominating to weight percent chlorine or bromine
Can be. The halogenated polymer is then obtained
From about 1.05 to about 1 mole per mole of halogenated polymer
1.25, preferably 1.06-1.20, for example 1.10
Sufficient unsaturated acid or anhydrous to contain moles of unsaturated acid
At 100-250 ° C, usually about 140-180 ° C
About 0.5 to 10 hours, for example 3 to 8 hours
it can. This general type of method is described in U.S. Pat.
No. 87,436, No. 3,172,892, No. 3,
272,746 and the like. Alternatively, olefin polymers and unsaturated
The acid substance is mixed and added while adding chlorine to the hot substance.
Get heated. A method of this type is described in U.S. Pat.
No. 707, No. 3,231,587, No. 3,91
No. 2,764, No. 4,110,349, No. 4,2
No. 34,435 and British Patent No. 1,440,219.
It has been disclosed. Usually the use of halogen
About 65 to 95 weight percent of an olefin such as polyisobutylene
% React with the dicarboxylic acid material. Halogen or catalyst
Performing the thermal reaction without using it usually results in polyisobutylene.
Only about 50-75% by weight of the resin reacts. Chlorination is anti-
Help improve responsiveness. For convenience, the above 1.0
5: 1.25, 1.06: 1.20 and 1.10: 1.
20 dicarboxylic acid forming units to polyolefin functionality
The valence ratio is based on the polyolefin used to make the product.
Total amount, ie, reacted and unreacted polyolefins
Based on the total amount of [0013]Nitrogen and alcohol ashless dispersant derivatives Useful for neutralizing hydrocarbyl-substituted dicarboxylic acid substances
The min compound has about 2 to 60, for example, 3 to 20
Total number of carbon atoms and about 1 to 12 e.g. 2 to 8 nitrogen atoms
Includes mono- and polyamines with numbers. These
The min may be a hydrocarbylamine, or other
Groups such as hydroxyl, alkoxy, amide,
Hydrocarbylamine containing tolyl and imidazoline groups
It may be. 1-6 hydroxyl groups, preferably 1
Hydroxyamines with ~ 3 hydroxyl groups are particularly
Useful. Preferred amines have the general formula Embedded image Wherein R, R ′ and R ″ are each hydrogen, C₁ ~ C_{twenty five}
Linear or branched alkyl group, C₁ ~ C₁₂Alkoxy C_Two
~ C₆ Alkylene group, C_Two ~ C₁₂Hydroxyaminoal
Kilen group and C₁ ~ C₁₂Alkylamino C_Two ~ C₆ Al
Selected from the group consisting of kylene groups, each s is from 2 to 6
Or the same or different numbers from 2 to 4, and t
Is a number from 0 to 10, preferably from 2 to 7].
Aliphatic saturated amines. [0014] Examples of suitable amine compounds include, but are not limited to:
But not 1,2-diaminoethane, 1,3-
Diaminopropane, 1,4-diaminobutane, 1,6-
Diaminohexane, polyethylene-amine such as diethyl
Lentriamin, triethylenetetramine, tetraethyl
Lenpentamine, polypropyleneamine, e.g., 1,2-
Propylenediamine, di (1,2-propylene) tria
Min, di (1,3-propylene) triamine, N, N-
Dimethyl-1,3-diaminopropane, N, N-di (2
-Aminoethyl) ethylenediamine, N, N-di (2-
(Hydroxyethyl) -1,3-propylenediamine, 3
-Dodecyloxypropylamine, N-dodecyl-1,
3-propanediamine, trishydroxymethylamino
Methane (THAM), diisopropanolamine, die
Tanolamine, triethanolamine, mo-, di- and
Tritamine, aminomorpholine such as N- (3
-Aminopropyl) morpholine and the like. [0015] Other useful amine compounds are 1,4-di-
Alicyclic diamides such as (aminomethyl) cyclohexane
, Heterocyclic nitrogen compounds such as imidazoline, and general
formula Embedded image Wherein G is hydrogen and Ω-amino of 1 to 3 carbon atoms.
Each selected from the group consisting of alkylene groups, and
p is an integer of 1 to 4].
Gin. Examples of such amines are limited
Although not intended, 2-pentadecyl imidazoline, N-
(2-aminoethyl) piperazine and the like. Commercially available mixtures of amine compounds are also beneficially used.
Can be For example, to produce an alkylene amine
One method for alkylene dihalide (ethylene
Dichloride or propylene dichloride)
Reacts with a nitrogen to form a pair of nitrogen atoms with an alkylene group
Obtain a complex mixture of linked alkylene amines, thus
Diethylene triamine, triethylene tetramine,
Such as tetraethylenepentamine and piperazine isomers
Forming a compound. Nitrogen atoms per molecule
On average about 5-7 low cost poly (ethyleneamine)
The compound is “polyamine H”, “polyamine 400”,
Under trade names such as "Dow Polyamine E-100"
Available on the market. Further, useful amines include those represented by the formula (i) Embedded image Wherein m has a value of about 3 to 70, preferably 10 to 35.
And formula (ii) Embedded image Wherein n has a value of about 1 to 40, provided that n
The sum of all is from about 3 to about 70, preferably from about 6 to about 35.
And R is up to 10 carbons having a valency of 3 to 6.
Which are polyvalent saturated hydrocarbon radicals of elementary atoms]
Oxyalkylene polyamines are exemplified. Equation (i) or
Represents an alkylene group in either of (ii) of about 2 to 7
Straight or branched, preferably containing about 2 to 4 carbon atoms
It can be a chain. Polyoxyalkylene polyamine of the above formula
Preferably polyoxyalkylenediamine and polyoxy
Sialkylenetriamines are preferred from about 200 to about 4,000.
Preferably an average molecular weight in the range of about 400 to about 2,000
May be provided. Preferred polyoxyalkylene polyamido
Has an average molecular weight in the range of about 200 to 2,000.
Polyoxyethylene and polyoxypropylene dia
Including min and polyoxypropylene triamine
You. Polyoxyalkylene polyamines are commercially available
Noh, for example, Jefferson Chemical Company
Trade name "Jeffamine" from Knee Inc.
D-230, D-400, D-1000, D-200
0, T-403 "and the like. The amine is 5-95% by weight of dicarboxylic acid
The oil solution containing the substance is removed until the desired amount of water is removed.
At about 100-250 ° C., preferably 125-175 ° C.
Generally, heating for 1 to 10 hours, for example, 2 to 6 hours
Thus, dicarboxylic acid materials such as alkenyl succinic anhydride
Reacts easily with objects. Heating is better than amides and salts
Promotes the formation of white imide or a mixture of imide and amide
It is preferred to be implemented as follows. The reaction ratio is the reaction
The amount of excess amine, the type of bond formed, etc.
Can vary considerably. Dicarboxylic acid partial content
For example, generally per mole of grafted maleic anhydride content
Is 0.3 to 2 mol, preferably about 0.3 to 1.0 mol
For example, 0.4 to 0.8 moles of amine such as
Used. For example, if one mole of olefin is olefin 1
To add 1.10 moles of maleic anhydride groups per mole
Reacted with maleic anhydride. Amides and imides
When converted to a mixture with
0.55 mole of amine per mole of dicarboxylic acid moiety
Preferably, 0.50 mole of amine is used. [0020] Nitrogen-containing dispersants are disclosed in US Pat.
7,936 and 3,254,025
Further processing by boriding as taught
Wear. This is about boron per mole of acylated nitrogen compound.
Nitrogen atom in acylated nitrogen compound from 0.1 atomic ratio
Amount that provides up to about 10 atomic percent boron per fraction
Oxides, boron halides, boron acids and boron
Boron compounds selected from the group consisting of esters of acids
Easily by treating the above acyl nitrogen dispersant with
Achieved. Advantageously, the dispersants of the present invention are boronated
From about 0.05 to 2.0, based on the total weight of the syl nitrogen compound
% Boron, for example 0.05 to 0.7% by weight
You. Dehydrated boric acid polymer (mainly (HBO
_Two )_Three ) Is considered to be present as a dispersant
Amide salts such as meta-
It is believed to bind as a borate salt. In the boron treatment, the acyl nitrogen compound is treated with about 0.1%.
0.5 to 4% by weight, for example, 1 to 3% by weight (the acyl nitrogen compound
(Based on the weight of the product)
Add the acid (which is usually added as a slurry)
Then, at about 135 ° C to 190 ° C, for example, 140 to 1 under stirring.
Heat at 70 ° C. for 1-5 hours and then heat
Easily implemented by stripping with
You. Alternatively, boron treatment involves removing boric acid while removing water.
To the hot reaction mixture of the carboxylic acid substance and the amine.
And can also be implemented. Tris (hydroxy
Methyl) aminomethane (THAM)
In response, as taught in GB 984,409.
Forming amide, imide or ester type additives
Or, for example, US Pat. No. 4,102,798,
Nos. 4,116,876 and 4,113,639
Oxazoline compounds and boronated
A xazoline compound can be formed. Further, the ashless dispersant may be the above-mentioned long-chain hydrocarbon residue.
Substituted dicarboxylic acid materials and mono- and polyhydric alcohols
Hydroxy compounds or phenols and naphthols
Esters derived from aromatic compounds, etc.
No. Polyhydric alcohols are the most preferred hydroxy compounds
And preferably from 2 to about 10 hydroxy
Group containing ethylene glycol, diethylene glycol,
Recall, triethylene glycol, tetraethylene glycol
Recol, dipropylene glycol, and alkylene groups
Other alkyl groups containing from 2 to about 8 carbon atoms
It is len glycol. As other useful polyhydric alcohols
Glycerol, glycerol monooleate,
Glycerol monostearate, glycerol mono
Methyl ether, pentaerythritol, dipentaery
Sultol and the like. Further, the ester dispersant is allyl alcohol.
, Cinnamyl alcohol, propargyl alcohol,
1-cyclohexane-3-ol and oleyl alcohol
Can also be derived from unsaturated alcohols such as
Of alcohols capable of forming the esters of the invention
Still other groups include, for example, one or more oxyalkylenes,
Minoalkylene or aminoaryleneoxyarylene
Oxyalkylene having a group, oxyarylene-,
Aminoalkylene- and aminoarylene-substituted alcohols
Ether alcohol and amino alcohol
Include. These are Cellosolve,
Toll (Carbitol), N, N, N ', N'-tetrahydro
Xytrimethylene diamine, and alkylene groups of 1 to about
Oxyalkylene groups containing 8 carbon atoms
By ether alcohols having up to about 150
Is shown. The ester dispersant is a diester of succinic acid.
Or acidic esters, ie, partially esterified succinic acids, and
Partially esterified polyhydric alcohol or phenol, ie free
Alcohols or phenolic hydroxyl groups
It can be a stele. Similarly, of the esters exemplified above
Mixtures are also contemplated within the scope of the present invention. Ester dispersant
Is exemplified, for example, in US Pat. No. 3,522,179.
Manufactured by one of several known methods, such as
Can be. The above long-chain hydrocarbon-substituted dicarboxylic acid substance
Can react with to form a dispersant
As the amine, 2-amino-1-butanol, 2-a
Mino-2-methyl-1-propanol, p- (β-hydr
Roxyethyl) anilyl, 2-amino-1-propano
3-amino-1-propanol, 2-amino-2-
Methyl-1,3-propanediol, 2-amino-2-
Ethyl-1,3-propanediol, N- (β-hydro
(Xypropyl) -N ′-(β-aminoethyl) piperazine
Tris (hydroxymethyl) aminomethane (Tris
Methylolaminomethane), 2-amido
No-1-butanol, ethanolamine, β- (β-
Droxyethoxy) ethylamine and the like.
You. Mixtures of these or similar amines can also be used.
Wear. A preferred dispersant is a succinic anhydride group.
Substituted and polyethyleneamines such as tetraethylene
Pentamine, pentaethylenehexamine, polyoxye
Tylene and polyoxypropylene amines such as polyoxy
Cypropylenediamine, trismethylolaminomethane
And pentaerythritol and combinations thereof
Derived from reacted polyisobutylene
You. One particularly preferred dispersant combination is disclosed in US Pat.
As described in No. 3,804,763, (A)
Polyisobutylene substituted with succinic anhydride groups,
(B) a hydroxy compound reacted therewith, such as pentane
Erythritol and (C) polyoxyalkylene polya
Min, such as polyoxypropylene diamine, and (D)
Polyalkylenepolyamines such as polyethylenediamine and
And tetraethylenepentamine,
(A) about 0.3 mol each of (B) and (D) per mole
About 2 moles and about 0.3 to about 2 moles of (C)
Including. Another preferred dispersant combination
Is described in US Pat. No. 3,632,511.
In addition, (A) polyisobutenyl succinic anhydride and (B)
Polyalkylenepolyamines such as tetraethylenepentami
And (C) polyhydric alcohol or polyhydroxy-substituted fat
Primary amines such as pentaerythritol or trisme
Includes combinations with tyrolaminomethane. [0026]Metal rust inhibitor and detergent Metal-containing rust inhibitor and / or detergent is ashless dispersion
Often used with agents. Such detergents and rust inhibitors
Additives include metal salts of sulfonic acids, alkylphenols,
Sulfurized alkylphenols, alkyl salicylates, naphthe
Nitrate and other oil-soluble mono- and dicarboxylic acids
I do. Highly basic or overused, often used as a detergent
Basic metal salts tend to interact specifically with ashless dispersants
There seems to be. Usually, these metal-containing rust inhibitors are added
The weight of the total lubricating composition in the lubricating oil
0.01 to 10% by weight, for example, 0.1 to 5 times
Used in amounts of% by volume. The highly basic alkaline earth metal sulfonate is
Often used as a detergent. These are usually oil
Mixtures containing soluble sulfonates or alkaryl sulfonic acids
Compound is required for complete neutralization of sulfonic acids present
Also heat with excess alkaline earth metal compound, and
After that, the excess metal is reacted with carbon dioxide to obtain the desired excess metal.
Form dispersed carbonate complex by providing basification
It is manufactured by forming. This sulfonic acid is
From a petroleum fractionation by distillation and / or extraction
Sulfolation of alkyl-substituted aromatic hydrocarbons such as those obtained
By honation or, for example, benzene, toluene, xy
Len, naphthalene, diphenyl and their halogen derivatives
Conductors such as chlorobenzene, chlorotoluene and chloro
Obtained by alkylating naphthalene,
Obtained by alkylation of aromatic hydrocarbons such as A
For example, about 3 to 30 or less such as haloparaffin
Dehydration of paraffins, alkylating agents with above carbon atoms
Olefins that can be obtained by
Polyolefins such as polymers from ethylene, propylene, etc.
Can be carried out in the presence of a catalyst. alkali
Sulphonate is usually used per alkyl-substituted aromatic moiety
About 9 to about 70 or more carbon atoms, preferably about 1
Contains from 6 to about 50 carbon atoms. By neutralizing these alkaryl sulfonic acids,
Can be used to provide the sulfonate
Potassium earth metal compounds include magnesium and calcium.
And barium oxides, hydroxides, alkoxides, charcoal
Acid salts, carboxylates, sulfides, hydrosulfides, nitrates, salts
Acid salts and esters. These examples are
Calcium, calcium hydroxide, magnesium acetate and
It is magnesium oxalate. As mentioned above,
Lithium earth metal compounds are completely contained in alkaryl sulfonic acid.
Used in excess than required for sum. Generally,
Although the amount is in the range of about 100-220%,
At least the stoichiometric amount of metal required for complete neutralization
It is also preferable to use 125%. Basic alkaline earth metal alkaryl sulf
Various other methods of making honates are described, for example, in US Pat.
50,088 and 3,150,089
Known, where overbasing is a hydrocarbon solvent-dilution
Alkoxide-carbonate complex in a dispersant oil
Achieved by hydrolysis with caryl sulfonate
Is done. Preferred alkaline earth sulfonate additives are
Based on the total weight of the additive system dispersed in the mineral lubricating oil
Of magnesium sulfonate in the range of about 25 to about 32% by weight
Total base number in the range of about 300 to about 400 with the
A magnesium alkyl aromatic sulfonate having
You. Neutral metal sulfonates are combined with rust inhibitors.
Often used. Polyvalent metal alkyl salicylate
And naphthenate materials are known additives for lubricating oil compositions.
Agents to improve their high temperature performance and to piston
This is to prevent the adhesion of carbonaceous material on
No. 2,744,069). Polyvalent metal alkyl salicy
The increase in the pre-basicity of the naphthenate and of the rate₈ ~
C₂₆A mixture of alkyl salicylate and phenate
Lucari earth metals such as calcium salts (U.S. Pat.
44,069) or polyvalent metal salts of alkyl salicylic acids
Can be achieved by using The acid
Is the alkylation of phenol followed by phenation,
Obtained by carboxylation and hydrolysis (US Patent
(No. 3,704,315) then commonly known and used
Can be converted to highly basic salts by the technology used.
Wear. The preliminary basicity of these metal-containing rust inhibitors is
It is beneficial to be at a TBN level of about 60-150.
Among useful polyvalent metal salicylates and naphthenate substances
Include alkyl-substituted salicylic acid or naphthenic acid or
Either one or both of them and an alkyl-substituted pheno
And sulfur readily derived from mixtures with
Crosslinking materials are included. Basic sulphide salicylate and its
These processes are described in U.S. Pat. No. 3,595,791.
Have been. Such a substance has the general formula Embedded image [Wherein, Ar is an aryl group having 1 to 6 rings,
R₁ Is from about 8 to 50 carbon atoms, preferably 12 to 30
An alkyl group having the carbon atom (optimally about 12)
X is sulfur (-S-) or methylene (-CH_Two −) Frame
A bridge, y is a number from 0 to 4 and n is a number from 0 to 4
Alkaline earth metals of aromatic acids having the formula
Nesium, calcium, strontium and barium salts
Is mentioned. Overbased methylene bridged salicylate-fe
The production of the naat salt follows the alkylation of phenol followed by
Phenation, carboxylation, hydrolysis, alkylene
Methylene bridges with coupling agents such as dihalides
By conventional techniques such as subsequent carbonation and simultaneous salt formation
It is easily implemented. In the present invention, 60 to 150
Having TBN and a general formula Embedded image Methylene-bridged phenol-salicylic acid
Cium salts are very useful. The metal sulfide phenate is "phenolsulfur
Can be considered as "metal salts of chlorides,"
General formula Embedded image (Where x = 1 or 2, n = 0, 1 or 2)
Metal salt (neutral or basic) of a representative compound, or
A polymer form of the compound (where R is an alkyl group)
And n and x are each an integer from 1 to 4;
In order to ensure proper solubility in the
The average number of carbon atoms in is at least about 9)
means. Each R group is preferably 5 to 40, preferably
It can contain from 8 to 20 carbon atoms. Metal salt
Converts alkylphenol sulfide to metal sulfide phena
Metal in an amount sufficient to impart the desired alkalinity to the sheet
It is produced by reacting with the contained substances. Useful alkyl sulfides regardless of production mode
Phenol is based on the weight of sulfurized alkylphenol
Generally about 2 to about 14% by weight, preferably about 4 to about 12%.
Contains by weight sulfur. Sulfurized alkylphenols
The phenol is neutralized and, if desired, a procedure well known in the art.
Overbasing the product to the desired alkalinity
Metals, including oxides, hydroxides and complexes in sufficient quantities
It can be converted by reaction with the contained substances. Good
A good method is to dissolve the metal in glycol ether
This is a neutralization method using a solution of Neutral or standard metal sulfide phenates are metals
Such that the ratio of phenol nucleus to phenol is about 1: 2
You. "Overbased" or "basic" metal sulfide phenates
Means that the ratio of metal to phenol is greater than the stoichiometric amount
Metal sulfides, for example, basic metal sulfides
Dodecyl phenate is an oil-soluble or dispersible form of excess metal.
(CO)_Two And depending on the reaction with)
Gold present in the corresponding standard metal sulfide phenate of the roller
It has a metal content in excess of 100% over the genus. Ashless content
Another group of additives that can interact with powders is
Often used as an abrasive additive and has antioxidant activity
Metal dihydrocarbyl dithiophosphate that also provides
You. The zinc salt is present in an amount of 0.1% based on the total weight of the lubricating oil composition.
Lubricating oil in an amount of 10 to 10% by weight, preferably 0.2 to 2% by weight
Most commonly used during These are known technologies
Therefore, usually alcohol or phenol and P_Two S_Five With
The reaction first forms dithiophosphoric acid and then the dithiophosphoric acid.
Produced by neutralizing phosphoric acid with a suitable zinc compound
Can be Of primary and secondary alcohols
It is possible to use mixtures of alcohols, including mixtures
However, secondary alcohols generally have improved wear resistance.
For imparting and primary alcohol is enhanced
Imparts improved thermal stability. Particularly useful is a mixture of the two
It is. Generally, any basic or neutral zinc compound
Can be used, but oxides, hydroxides and
Carbonates are most commonly used. Commercial additives are medium
By using an excess of basic zinc compound in the summation reaction
It often contains excess zinc. Dihydrocarbyl di useful in the present invention
Zinc thiophosphate is the dihydrocarbyl ester of dithiophosphate.
Is an oil-soluble salt of Embedded image [Wherein, R and R ′ are 1 to 18, preferably 2 to 12
Or different hydrocarbyl containing two carbon atoms
And may be an alkyl, alkenyl, aryl
Aralkyl, alkaryl and cycloaliphatic radicals
And a group comprising R and
Particularly preferred as R 'groups are those having 2-8 carbon atoms
Is an alkyl group containing Thus, this group is
For example, ethyl, n-propyl, i-propyl, n-butyl
I-butyl, sec-butyl, amyl, n-hexyl,
i-hexyl, n-octyl, decyl, dodecyl, oct
Tadecyl, 2-ethylhexyl, phenyl, butylphen
Nil, cyclohexyl, methylcyclopentyl, prope
Nyl, butenyl and the like. To get oil solubility
Is the total number of carbon atoms (i.e., R and R ') in dithiophosphoric acid.
The number is generally about 5 or more. [0036]Composition Dispersant product of the present invention, i.e., a dicarboxylic acid forming substance
Amines or alcohols on the dicarboxylic acid-forming substance itself or
And amino alcohols, their mixtures, etc.
The lubricating product is a lubricating oil composition, such as an automotive crankcase.
About 0.01% by weight of the total composition in
To 15% by weight, for example, 0.1 to 10% by weight, preferably 0.1 to 10% by weight.
It can be blended at a concentration within the range of 2 to 7.0% by weight.
You. A lubricant to which the product of the present invention can be added
In addition to hydrocarbon oils derived from petroleum,
Alkyl ethers of rubonic acid, polyglycol
Stele, poly-α-olefin, alkylbenzene, phosphoric acid
Synthetic oils such as organic esters and silicone oils
I can do it. The product of the present invention is treated with gasoline and about 150
Middle distillate oils having boiling points in the range of ８００800 ° F., for example
Kerosene, diesel fuel, home heating fuel, jet fuel
As a dispersant in petroleum fuels that are normally liquid, such as
When used, based on the weight of the total composition in the fuel
0.001 to 0.5% by weight, preferably about 0.001
Additive concentrations in the range of ~ 0.1% by weight are commonly used.
You. This additive comprises 5 to 70% by weight of dispersant and 95 to
Conveniently dispensed as a concentrate containing 30% oil by weight
Can be Usually in the presence or absence of other additives
Without adding a small amount of additives, for example, up to 5 to 50% by weight.
Dissolved in a proportion of, for example, 50 to 95% by weight of mineral lubricating oil.
It is. This dispersant is also a lubricant additive package feature.
Can be used even if it contains a metal detergent
it can. These packages are generally about 20-8
0% by weight mineral lubricating oil and about 20-80% by weight e.g.
Contains 40-60% by weight of dispersant. This package
Further comprises about 3 to 50, for example 3 to 40, preferably 5 to 2
5 Containing, for example, 10 to 20% by weight of a metal detergent
Can be. It may also be about 3-40, preferably 5-2.
5 containing, for example, 10 to 20% by weight of zinc dithiophosphate
You can also. Dispersant, metal detergent and zinc dithiophosphate
All additive weight percentages are based on the total weight of the additive package
Follow. The above composition, concentrate or package includes:
Other conventional additives such as pour point depressants, tricresyl phosphate
Or an anti-wear additive such as zinc dithiophosphate;
Ru-α-naphthylamine, t-octylphenolsulfur
Fide, 4,4'-methylenebis (2,6-di-t-butyl
Antioxidants, such as ethylene glycol
Len copolymer, polymethacrylate, polyisobutylene
Viscosity, such as alkyl, fumarate / vinyl acetate copolymer, etc.
Degree index improver, amine, hydroxyamine, poly
No other polyisobutylene succinic acid reacted with all
Other ashless dispersants such as water can also be included. [0039] The present invention includes preferred embodiments of the present invention.
It will be better understood by reference to the following examples.
All parts are parts by weight unless otherwise noted.
is there.Example 1 Part A 100 parts of polyisobutylene and 7.55 parts of anhydrous maleic
By heating the mixture with the acid to a temperature of about 220 ° C.
The polyisobutylene (PIB) molecule of 1725Mn
SA: PI with per succinic anhydride (SA) moiety 1.04
Polyisobutenyl succinic anhydride having a B ratio (PIB
SA) was prepared. When the temperature reaches 120 ° C, salt
Start the sulfur addition and add 5.88 parts of chlorine to the hot mixture.
Was added at a constant rate for about 5.5 hours. Then the reaction mixture
The mixture was digested at 220 ° C for about 1.5 hours (heat saw
King), then strip with nitrogen for about 1 hour
Was. The resulting polyisobutenylsuccinic anhydride was 64.
Had an ASTM saponification value of 2 as follows:
1.04 succinic anhydride calculated based on the starting PIB
Corresponds to (SA) to polyisobutylene (PIB) ratio. [0040] (Equation 1) The PIBSA product contains 83.8% active ingredient (ai) by weight.
% And the balance was mainly unreacted PIB. 1.
The SA: PIB ratio of 04 was charged to the reactor as starting material
All PIBs contained, ie, reacting PIBs and unreacted
Based on both remaining PIBs. [0041]Part B Amination of Part A PIBSA as follows
Simplification. In a reaction flask, 1,800 g of 6
PIBSA with a saponification number of 4.2 and 1,317 g
S150N lubricating oil (about 150SUS at 100 ° C)
Neutralized oil having a viscosity of about 149 ° C.
Heated. Then, 121.9 g of commercial grade polyethylene
Renamine (hereinafter referred to as PAM) (this is the molecular equivalent
Polyethylene containing about 5 to 7 nitrogen atoms on average
Mixture was added, and the mixture was added to 1
Heat to 49 ° C for about 1 hour, then soak with nitrogen for about 1.5 hours.
Tripped. Next, do not heat with stirring at 163 ° C.
49 g of boric acid are added over about 2 hours, then
Strip with nitrogen for 2 hours, then cool and filter
To give the final product. The product is kept at 100 ° C.
With a viscosity of 428 cs, a nitrogen content of 1.21% by weight,
Has a boron content of 0.23% by weight and
% Reaction product, ie, the substance actually reacted and 50.7%
Contains unreacted PIB and mineral oil (S150N) by weight
Was. [0042]Example 2 A SA: PIB ratio of 1.26 was obtained in a similar manner to Part A of Example 1.
PIBSA with the exception that 100 parts of poly
Isobutylene was added to 7.40 parts of chlorine and 10.23 parts of
Reaction with water maleic acid. PIBSA has a 76.7
Having a saponification value and 87.3% by weight of the active ingredient.
Was. 1,800 g of PIBSA (saponification number 76.7)
About 1,462 g S150N oil and 145.7 g PA
M and then heated to 149 ° C. for 1 hour,
Strip for 1.5 hours, then 51.5g
Add acid and heat at 163 ° C. for 2 hours, then add additional nitrogen
Strip for 2 hours, then cool and filter
Was. The final product is 1.41 wt% N, 0.23 wt%
% B and 52.8% by weight of the reaction product.
And had a viscosity of 458 cs at 100 ° C. [0043]Example 3 SA: PIB ratio of 1.41 in the general manner of Part A of Example 1
With the exception that 11.63 parts
Of maleic anhydride in 100 parts of 1725 Mn polyiso
Mix butylene and add 8.42 parts of chlorine for 4.5 hours
Sprayed over. PIBSA is 84.8 Ken
About 90.3% by weight of the active ingredient
The corresponding PIB was 9.7% by weight. 1,800g PI
BSA (SA: PIB ratio of 1.41) with 1,536 g
Diluted with S150N oil, 161.1 g of the above PAM and 1
The reaction was carried out at 49 ° C. for 1 hour and then
I hopped. Then, at 163 ° C. with stirring.
8 g of boric acid are added over 2 hours and then nitrogen is added for 2 hours.
Stripped for hours, cooled and filtered. Product
Contains 1.49% by weight N and 0.22% by weight B
And has a viscosity of 574 cs at 100 ° C., and
It contained 52.8% by weight of the reaction product. [0044]Example 4 100 parts of polyisobutyle as in Part A of Example 1
(1725Mn) with 8.12 parts of maleic anhydride
And then add 6.29 parts of chlorine over 5.5 hours
With the addition, a SA: PIB ratio of 1.13 was obtained.
PIBSA was manufactured. PIBSA has a 69.3
Has a saponification value and contains 85.2% by weight of active ingredient
Was. 1,800 parts of PIB in the same manner as in Example 3
SA (SA: PIB ratio of 1.13, activity of 85.2% by weight)
Is diluted with 1,350 parts of S150N oil, and 11
Reaction with 8 parts of PAM at 149 ° C. for 1 hour and with nitrogen
Stripped for 1.5 hours. Then, at 163 ° C,
1.5 hours of 39.2 parts of boric acid with tripping
And then strip with nitrogen for 2 hours
Then it was filtered. The final product is 1.24% by weight N,
Containing 0.25% by weight of B and 463 at 100 ° C.
cs and 49.1% by weight of the reaction product
Contained. [0045]Example 5 SA: PIB ratio of 0.97 in the general manner of Part A of Example 1
Was prepared, but with 5.47 parts of
6.9 by adding chlorine over 5.5 hours.
8 parts of maleic anhydride to 100 parts of polyisobutylene
(Molecular weight 1.725). PIBS obtained
A has a saponification number of 59.6 and the active ingredient is 7
It was 9.7% by weight. 1,800g of PIBSA
Mix with 1,162 g of S150N oil and add 113.2 g
Reaction with PAM at 149 ° C. for 1 hour, then with nitrogen for 1.
Stripped for 5 hours. After this, 46 g of boric acid
Is added at 163 ° C. over 2 hours, then 1
Stripped at 63 ° C. for 2 hours. Final production after filtration
Contains 1.20 wt% N, 0.24 wt% B
And has a viscosity of 475 cs at 100 ° C., and 55.
It contained 6% by weight of the reaction product. [0046]Additive interaction test 12.5 g of metal detergent in 50 g of the product of Examples 1 to 5 and
Mix 12.5 g of S150N oil and reduce its viscosity
Initially and after 24 hours and 168 hours at 100 ° C
Measuring the product to the additive interaction effect
Was tested. In the above test, two metal detergents
Was used. Detergent A is about 9% by weight magnesium lubricating oil
400TBN (Total Base Number) overbased sulfonic acid additive
It was magnesium. Detergent B is about 12% by weight
300TBN overbased sulfonic acid as a lubricating oil additive
It was calcium. About dispersant: detergent: oil ratio
A ratio of 4: 1: 1 does not result in a gel, but
Enough to distinguish between weak and weakly interacting systems
Only used to give great interaction. Also,
Many lubricating formulations have 3 or 4 times more dispersion than detergents
Have an agent. Table I below shows the compositions tested and the
This is a summary of the test results. [0047] [Table 1] The data in Table I shows that the SA: PIB ratio is 0.9.
7 Minutes as SA: PIB ratio changes to 1.41
Demonstrates improved interaction between powder and metal detergent
doing. Interaction as measured by viscosity increase
Accelerates at a ratio of 1.41. The invention relates to Table I
Represented by Example 4, which has an SA of 1.13:
Within the scope of the present invention in PIB ratio and
Provided low interaction with metal detergents. [0049]Example 6 Polyisobutylene having a number average molecular weight of about 2,250
From a polyisobute having a SA: PIB ratio of 1.09
Nilsuccinic anhydride was produced. This PIBSA is Example 1
Was produced in the same manner as in Part A, except that
Part polyisobutylene is about 5.67 parts chlorine and about 6.67 parts.
Reacted with 97 parts of maleic anhydride. The resulting poly
Sobutenylsuccinic anhydride has a saponification number of about 52
I was 1,800 copies of PIBSA and 1,163 copies of S
Blended with 150N oil and 94 parts PAM. Mix 1
Heat to 49 ° C. for 1 hour and at this temperature with nitrogen
Stripped for 1.5 hours. Stirring at 163 ° C
36.5 parts of boric acid are added over 1.5 hours.
Then strip with nitrogen for 2 hours, cool and filter
did. The product contains about 0.97% by weight N and about 0.28%.
It contained B wt%. [0050]Example 7 Polyisobutylene having a number average molecular weight of about 1,950
From a polyisobu having an SA: PIB ratio of about 1.15
Thenylsuccinic anhydride was prepared. This PIBSA is an example
1 was prepared in a similar manner to Part A, except that about 6.5
3 parts of chlorine and about 8.02 parts of maleic anhydride are used.
Was. The resulting polyisobutenyl succinic anhydride is about
It has a saponification number of 62.5 and the active ingredient is about 84.
It was 4% by weight. 1,800 copies of PIBSA 1,3
Mix with 28 parts S150N oil and 104 parts PAM,
Heat to 149 ° C. for 1 hour and blow nitrogen for 1.5 hours
And stripped. Then 163
38 hours of boric acid in 1.5 hours while mixing at a temperature of
Added all over. After this, strip for 2 hours with nitrogen
And cooled and filtered. The final product is about 1.08
% N and 0.26% B by weight. [0051]Example 8 Polyisobutylene having a number average molecular weight of about 2,600
From a polyisobu having an SA: PIB ratio of about 1.15
Thenyl succinic anhydride (PIBSA) was produced. this
PIBSA was prepared in a similar manner to Part A of Example 1, but
However, 4.9 parts of chlorine and 6 parts of maleic anhydride are used.
Was done. The resulting polyisobutenyl succinic anhydride is
It has a saponification number of about 43.6 and the active ingredient is about 73
%. 99.2 copies of 1,800 copies of PIBSA
Of S150N oil and 83.3 parts of PAM
Heat to 9 ° C for 1 hour and blow nitrogen for 1.5 hours.
And stripped. Then, the temperature of 163 ° C.
56 parts of boric acid for 1.5 hours
Added. After this, strip with nitrogen for 2 hours,
Cooled and filtered. The final product is about 0.96 weight
% N and about 0.33% by weight B. [0052]Example 9 Polyisobutylene having a number average molecular weight of about 2,600
From polyisobute having a SA: PIB ratio of 1.25
Nilsuccinic anhydride was produced. This PIBSA is Example 1
Was prepared in the same manner as part A, except that 6.00 parts
Of chlorine and 7.54 parts of maleic anhydride were used.
The polyisobutenyl succinic anhydride obtained was about 51.
A saponification number of 6 and the active ingredient is about 80% by weight.
Was. 1,800 copies of PIBSA and 1,328 copies of S1
Mix with 50N oil and 100.9 parts PAM, 149 ° C
Heating for 1 hour and blowing with nitrogen for 1.5 hours
By stripping. Then at a temperature of 163 ° C.
While mixing with 60 parts of boric acid for 1.5 hours.
Added. After this, strip with nitrogen for 2 hours,
Cooled and filtered. The final product is about 1.07 weight
% N and about 0.32% B by weight. [0053]Example 10 From polyisobutylene having a molecular weight of about 2,200,
Polyisobutenyl having a SA: PIB ratio of about 1.13
Produce succinic anhydride and then react with PAM and boric acid
About 0.25% by weight boron and about 1.0% by weight
Of a lubricating oil dispersant containing nitrogen. [0054]Engine test Example 11 Lubricant A Is 10W40 crankcase motor oil
And the PIB has a molecular weight of about 1,740;
SA: PIBSA whose PIB ratio or functional number is 1.19
Component produced by reacting PAM with PAM
To contain 4.5% by volume of the dispersant concentrate of the powder product
Was prescribed. PIBSA chlorinates PIB and then
Made by reacting with maleic anhydride. This
Analysis of the concentrate contains about 1.27% by weight N.
I was In addition, this formulation has improved hydrocarbon type viscosity index.
Agent, zinc dialkyldithiophosphate, overbased 400TBN
Also contains magnesium sulfonate, friction reducer and defoamer
Was.Lubricant BIs the same as the lubricant A
However, using PIB with a molecular weight of 1,300, about 1.
Made from PIBSA with 3: 1 SA: PIB ratio
A 4.5% by volume concentrated ashless dispersant was used.
Was. This PIBSA was reacted with PAM. This variance
When the concentrate of the agent is analyzed, it contains about 1.46% by weight of N.
Was. [0055] Lubricant A and B were added to MS sequence VD
Tested in the gin test. This test is
It is well known in the industry. this is,ASTM Document for Mu
ltigrade Test Sequence for Evaluating Automotive E
ngine Oil, Sequence VD, Part 3 of STP 315HDescribed in
Have been. At the end of each test, 0-1
A score is given on a scale of 0. In this case, 10 is perfect
Represents clean parts and adheres to smaller numbers
It indicates that the degree of formation of the object is high. Then, each grade
And average on a scale of 10 to perfect score
You. This test is for “stop-start” city driving and proper
1980 model under test conditions that simulate various temperature operations
It is implemented on a Ford 2.3-liter four-cylinder engine.
The results of the cleanliness obtained using the above composition are shown in Table II
You. [0056] [Table 2]Table II shows the 4.5% by volume used for the lubricant B.
Do not meet the required average varnish quantity of 6.6
Not enough to pass this test
It is shown. On the other hand, 4.5 of the dispersant concentrate of the present invention.
% By volume, even if it had a low nitrogen concentration
Also met all the required quantities for this test. In addition,
Lighting also improves performance compared to boronated dispersants
It is. Thus, a lubricant A 'similar to the lubricant A was prepared.
Except that PIB has a molecular weight of 1,687 and SA:
3. A boronated dispersant concentrate having a PIB ratio of 1.18.
5% by volume was used, and the dispersant was analyzed for 1.
Containing 21% by weight of nitrogen and 0.28% by weight of boron
I was Lubricant A 'had a sludge rating of 9.54;
98 average varnishes and 7.14 piston skirt crocodile
The score was shown. A lubricant B 'similar to the lubricant B was prepared.
Except that PIB has a molecular weight of 1,300 and SA:
3. A boronated dispersant concentrate having a PIB ratio of 1.31.
1.46% used by volume and the dispersant analyzed for 1.46
Contains nitrogen by weight and 0.32% by weight boron
Was. The same engine tee used to test lubricant A '
As an average of several tests on the strike, the lubricant B '
Has a sludge rating of 9.55, an average varnish of 6.63 and
And 7.06 piston skirt varnish. Different
Using a modified engine, lubricant B '(some tests
Average) is a sludge score of 9.50 and a flatness of 6.44.
Shows uniform varnish and 6.93 piston skirt varnish
Was. Thus, the lubricant A 'containing the dispersant of the present invention
Therefore, a good average varnish was obtained. The lubricant C is the same as the lubricant A.
With the proviso that it contains 4.0% by volume of the dispersant concentrate.
10W30 crankcase oil. Also lubricant
C is a small amount of viscosity depending on the required quantity of 10W30 viscosity.
An index improver was also needed. Lubricant D is the same as Lubricant C
Except that it was used in lubricant B
It contained 4.0% by volume of the dispersant concentrate. Lubricant C and
And D were tested in the Caterpillar 1-H2 test
But but “ASTM Document for Single Cylinder Engi
ne Test for Evaluating the Performance of Crankcas
e Lubricants, Caterpillar 1-H2 Test Method, Part
1, STP509AMore than the full 480 hour test described in
The filter was tested for 120 hours. This test is a
Diesel lubricant is fixed when operating on diesel engine
Assesses the ability to remove deposits of deposits on
You. [0059] [Table 3] Table III shows that the present invention used in Lubricant A
The dispersant is a top dispersant compared to the known dispersant in the lubricant A
Group Fill (TGF) and Weid Total
Disadvantage (WTD), that is, superior in deposits
Are shown. This advantageous comparison, even if all nitrogen
Compared to 1.46% by weight of nitrogen in the known dispersant concentrate
Lubricant A was obtained with only 1.27% nitrogen. Or
This, in turn, translates into costly polyamine formation in the dispersant.
Illustrate more efficient use of minutes. The boronated dispersant concentrate product of Example 4 was
Prepared in the same manner as Lubricant C except that 0% by weight was used
Caterpillar 1G-2 test for the lubricant C '
However, this test was conducted under theASTM Document fo
r Single Cylinder Engine Test for Evaluating the P
erformance of Crankcase Lubricants, Caterpillar1-G
2 Test Method, Part 1, STP 509AAll 4 listed in "
The test was performed for 120 hours rather than the 80 hour test. Ma
Lubricant D 'was also tested, which was similar to Lubricant D
(Provided that the boronated dispersant
The thick material has a molecular weight of 1,300 PIB and 1.31 S
A: Made using PIBSA having a PIB ratio
And the dispersant analyzed for 1.46% by weight N and
0.32% by weight of B). Lubricant C 'is 5
4 TGFs (Top Group Fill) and 339
Indicates WTD (Wade Total Demerit)
It is a lubricant with a TGF of 57 and a WTD of 324
It was almost comparable to D's. Tables II and III show gasoline engine tests.
Of dispersants in both diesel and diesel engine tests
Effective and form an improved dispersant.
High molecular weight polymer with high SA: PIB ratio
Illustrates the high engine performance that can be obtained by
You. Table I also shows that if the SA: PIB ratio is too high,
May cause unwanted viscosity increase and additive interaction
Indicates that there is a possibility. Thus, the present invention is based on the selection of the present invention.
Achieving an unexpected overall improvement in properties within a choice.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location // (C10M 159/12 129: 32 143: 00 145: 02 129: 04 133: 04) (C10M 169/04 149: 22 149: 02 135: 10 137: 06) C10N 10:02 10:04 30:04 40:25 60:00 (72) Inventor Malcolm Wodwoops Witchview, Westfield, NJ, USA Drive 7

Claims (1)

(57) [Claims] 5 to 70% by weight of a lubricating oil; (a) having a number average molecular weight of 1,500 to 5,000
Olefin polymer of C ₂ -C ₁₀ monoolefin and
Depending on the reaction of C ₄ -C ₁₀ monounsaturated acid material
The olefin polymerization formed and used in the reaction
1.05 to 1.25 dicarboxylic acids per molecule,
Hydrocarbyl-substituted C in which a hydrate or ester moiety is present
₄ -C ₁₀ dicarboxylic acid, an anhydride or ester material, (b) an amine, alcohol, amino alcohol and this
Reaction with a reactant selected from the group consisting of these mixtures
From 30 to 95% by weight of a dispersant consisting of the product.
Lubricant additive concentrate. 2. The dispersant replaces polyisobutylene with maleic anhydride.
The reaction formed with the polyamine
The concentrate for lubricating oil according to claim 1. 3. 1.0 per polyisobutylene part used in the reaction
3. The composition of claim 2, wherein there are 6 to 1.20 succinic anhydride moieties.
An additive concentrate for a lubricating oil as described. 4. Substances per mole of polyisobutylene used in the reaction
On average from 1.05 to 1.25 mol of succinic anhydride groups
Has a converted number average molecular weight of 1,500 to 5,000
2. The additive for lubricating oil according to claim 1, which is polyisobutylene.
Agent concentrate. 5. 3-50% by weight metal-containing detergent or rust inhibitor
The lubricating oil additive concentrate according to claim 1, further comprising: 6. Metal detergent is overbased alkaline earth metal sulfonate
The lubricating oil additive concentrate according to claim 5, which is a lubricant. 7. 3 to 40% by weight of zinc dihydrocarbyl dithiophos
2. The lubricating oil additive concentrate according to claim 1, further comprising a fate.
Stuff. 8. The lubricating oil of claim 1, wherein the dispersant is boronated.
Additive concentrate. 9. Metal-containing detergent or rust inhibitor is metal sulfonic acid
Salts, metal salicylates, metal naphthenates and the like
A metal salt selected from the group consisting of a mixture.
An additive concentrate for a lubricating oil as described. 10. If the metal containing detergent or rust inhibitor
N, barium, calcium, magnesium and
Alkaline earth selected from the group consisting of these combinations
The lubricating oil additive concentrate according to claim 9, which is a class of metals. 11. Metal-containing detergent or rust inhibitor is overbased sulfuric acid
Magnesium, overbased calcium sulfate and mixtures thereof
The lubricating oil according to claim 5, which is selected from the group consisting of a compound.
Additive concentrate. 12. Olefin polymer having a number of 1,600 to 3,000
2. The lubricating oil additive concentrate according to claim 1, which has an average molecular weight.
Stuff. 13. 5 to 70% by weight of fuel oil; (a) having a number average molecular weight of 1,500 to 5,000
Olefin polymer of C ₂ -C ₁₀ monoolefin and
Depending on the reaction of C ₄ -C ₁₀ monounsaturated acid material
The olefin polymerization formed and used in the reaction
1.05 to 1.25 dicarboxylic acids per molecule,
Hydrocarbyl-substituted C in which a hydrate or ester moiety is present
₄ -C ₁₀ dicarboxylic acid, an anhydride or ester material, (b) an amine, alcohol, amino alcohol and this
Reaction with a reactant selected from the group consisting of these mixtures
From 30 to 95% by weight of a dispersant comprising the product.
Additive concentrate for fuel oil. 14． Dispersant converts polyisobutylene with maleic anhydride
Then formed by reacting with a polyamine
The fuel oil additive concentrate according to claim 13. 15. 1 per polyisobutylene part used in the reaction.
Claims wherein from 06 to 1.20 succinic anhydride moieties are present.
14. The additive concentrate for fuel oil according to 13 above. 16. The substance is 1 mol equivalent of polyisobutylene used in the reaction.
1.05 to 1.25 moles of succinic anhydride groups on average
Has a substituted number average molecular weight of 1,500 to 5,000
14. The fuel oil according to claim 13, which is polyisobutylene.
Additive concentrate. 17． 14. The fuel according to claim 13, wherein the dispersant is boronated.
Additive concentrate for fuel oil. 18. Olefin polymer having a number of 1,600 to 3,000
14. The fuel oil additive concentrate according to claim 13, which has an average molecular weight.
Thick.